Chapter 5. Self-condensation of acetophenone

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1 Chapter 5 Self-condensation of acetophenone

5.1. Introduction D ypnone is a useful intermediate for the production o f a large range o f compounds. It has been used as a softening agent, plastisizer and perfiim ery base.

chloride, anhydrous hydrogen bromide, alum inum chloride, alum inum?

2 5.1. Introduction D ypnone is a useful intermediate for the production o f a large range o f compounds. It has been used as a softening agent, plastisizer and perfiim ery base. Dypnone has been prepared conventionally by the action of sodium ethoxide, alum inum brom ide, phosphorous pentachloride, alum inum triphenyl, zinc diethyl, calcium hydroxide, anhydrous hydrogen chloride, anhydrous hydrogen bromide, alum inum chloride, alum inum?er/-butoxide or hydrogen fluoride on acetophenone as described in the earlier literature [1-4], In addition, it has been obtained by the action o f aniline hydrochloride on acetophenone, followed by treatm ent with hydrochloric acid. Unfortunately, its synthesis is not always an easy task and Lewis acid catalysts have several disadvantages if applied to industrial processes such as wasting large am ounts o f catalysts, corrosion o f reactor, water pollution by acidic wastewater, and difficulty o f catalyst recovery. In addition, A IC I3 being a strong Lewis acid also catalyzes other undesirable side reactions such as poiycondensation o f ACP to a m ixture o f other products. In view o f the above, it was o f interest to develop a new solid catalyst for the selective synthesis o f dypnone. Modified zeolites are known to catalyze selectively aldol condensation o f ACP to dypnone [5-8]. The objective o f the present w ork is to replace the conventional Lewis acids catalyst with environm entally friendly solid acid catalysts such as sulfated zirconia (SZ) sulfated titania (ST) which are open structure and H-beta zeolite is closed three dimensional porous structure. We have chosen the later among other zeolites because it has been synthesized and characterized in our lab shows a good activity towards a variety o f acylation reactions [9-11] and halogenation reactions [12]. It has also been reported that a com parative study of SZ with H-beta zeolite for alkylation o f isobutene [13], Another objective is to enhance the selectivity for dypnone and to m inim ize the form ation o f consecutive products in the condensation o f ACP using solid acid catalysts. This paper 117

V Acid catalyst stirring, A + H2O acetophenone 5.2, Experimental Scheme 5.

3 presents the results o f a study comparing the perform ance o f sulfated metal oxides with H- beta catalyst in the condensation o f ACP (schem e 1). The condensation o f ACP to dypnone has not been reported yet using such catalysts. The influence o f catalyst concentration and reaction tem perature is also reported using SZ as catalyst. V Acid catalyst stirring, A + H2O acetophenone 5.2, Experimental Scheme 5.1 Acidity o f the catalysts was evaluated by the tem perature program m ed desorption o f ammonia from 303 K to 873 K (in several steps) using the m ethod described in the literature [14]. The physico-chem ical properties of the samples are given in Table 5.1. Before reaction, the catalysts were dehydrated at 573 K for 3 h. Table 5.1: Physico-chem ical properties o f catalysts Catalyst Sulfur content (w t% )" Surface area (m '/g )' N H 3 desorbed (mmol/g) at (K) N H 3 chem isorbed at 303 K (m m olg'') S04^- /Zr02 S0 4 ^- /Ti H-beta" ''m easured by SEM JEOL(JSM -5200); m easured by N 2adsorption (NOVA), c SiOi/A bos m olar ratio=26; degree of H^-exchange= >98.7%. 118

5.2.1. C atalytic reaction Reactions were performed in the liquid phase under batch conditions. In a typical reaction, the activated catalyst (0.5 g) was added to ACP (0.

The course o f the reaction was followed by analyzing the reaction mixture periodically using a gas-chrom atograph (HP 6890) equipped with a flame ionization detector (FID) and a capillary colum n

4 C atalytic reaction Reactions were performed in the liquid phase under batch conditions. In a typical reaction, the activated catalyst (0.5 g) was added to ACP (0.042 mol) and the resulting suspension was m agnetically stirred at 433 K. The course o f the reaction was followed by analyzing the reaction mixture periodically using a gas-chrom atograph (HP 6890) equipped with a flame ionization detector (FID) and a capillary colum n (HP 5% silicone gum). The products were also identified by GC/MS (Shim adzu, QP 2000 A) analysis. The isolation o f pure products was accomplished by silica gel ( mesh) colum n chrom atography with 5 % ethyl acetate in petroleum ether as eluting solvent. TLC and GC confirmed the form ation o f pure compound. The major products obtained in this study are in agreem ent with the spectroscopic data o f the pure compound. Spectroscopic data of dypnone: H N M R (200 M Hz) (C D C I3 ) (8); 2.48(s, 3H); 7.05(m, IH); (m, loh). GC-FT-IR (vapor phase); 1610 cm '' (-C=C-); 1675 cm ' (-C =0). The conversion is defined as the percentage o f ACP transform ed. The rate o f ACP conversion is given as the amount of ACP (mmol) converted per gram o f the catalyst per hour during the initial period. The selectivity (wt.%) for a product is expressed as the am ount o f the product divided by the amount of total products and m ultiplied by Results and discussion Effect o f various catalysts The catalytic activity, rate o f ACP conversion and selectivity to dypnone form ation with different catalysts, under similar reaction conditions, are given in Table 5.2. The results with A IC I3 are also included for comparison. As seen from Table 5.2, trans and cis dypnone together with ketene are formed in the condensation o f ACP. The aldol condensation o f ACP 119

produces dypnone as a major and primary product while ketene is a secondary product. As can be seen from Table 2, SZ and zeolite H-beta exhibit sim ilar and higher activity com pared to the ST.

1, 28.5, 40.8 wt.%, 6.7, 4.8, 6.8 m mol g '' h '' and 86, 86 and 85 wt. %, respectively. A IC I3 catalyst is found to be more active (180.5 mmol g '' h"') with com parable selectivity (84 wt.

5 produces dypnone as a major and primary product while ketene is a secondary product. As can be seen from Table 2, SZ and zeolite H-beta exhibit sim ilar and higher activity com pared to the ST. How ever, the selectivity for dypnone over all catalysts rem ains nearly constant. The conversion o f ACP, rate of ACP conversion and selectivity for dypnone over SZ, ST and H-beta are found to be 40.1, 28.5, 40.8 wt.%, 6.7, 4.8, 6.8 m mol g '' h '' and 86, 86 and 85 wt. %, respectively. A IC I3 catalyst is found to be more active (180.5 mmol g '' h"') with com parable selectivity (84 wt.%) to dypnone. The higher conversion o f ACP over SZ and H- beta seems to be due to the fact that these catalysts exhibit stronger acid sites (Table 5.1). Table 5.2. C ondensation o f acetophenone with various catalysts Catalyst Conversion of ACP (wt.%)^* Rate o f ACP conv. (mmolg^'h"')*^ Product distribution (wt. %) D ypnone Others'" S04^7Zr S04^7Ti H-beta AlCb^ " Reaction conditions: catalyst(g)=0.5; acetophenone(m ol) = 0.042; reaction tem perature (K) = 433; reaction time(h) = 5 Rate o f ACP conversion(mmolg 'h ') is expressed as the ACP converted per hour per g ram o f the catalyst Others = cis form o f dypnone and ketenes Reaction time (h) = 0.16 As can be seen from Table 5.2, SZ and zeolite H-beta exhibit similar and higher activity com pared to the ST. However, the selectivity for dypnone over all catalysts rem ains nearly constant. The conversion of ACP, rate o f ACP conversion and selectivity for dypnone over SZ, ST and H-beta are found to be 40.1, 28.5, 40.8 wt.%, 6.7, 4.8, 6.8 mmol g"' h"' and 86, 86 and 85 wt. %, respectively. AICI3 catalyst is found to be m ore active (180.5 mmol g''h" 120

These results indicate that strong acid sites are the m ost im portant factor to enhance both the protonation and the dehydration and consequently to force the aldol condensation o f ACP

6 ') with com parable selectivity (84 wt.%) to dypnone. The higher conversion o f ACP over SZ and H-beta seem s to be due to the fact that these catalysts exhibit stronger acid sites (Table 5.1). These results indicate that strong acid sites are the m ost im portant factor to enhance both the protonation and the dehydration and consequently to force the aldol condensation o f ACP to dypnone. Optimization o f the reaction condition was done with catalyst SZ and other catalysts w ere com pared under optimized conditions Duration o f the run Fig Effect o f different catalysts on conversion o f ACP (wt.%); Reaction conditions: catalyst (g)=0.5; acetophenone (mol) = 0.042; reaction tem perature (K) = 433; reaction time(h) =

The lower activity o f A IC I3 after 2 h may be attributed to the am ount o f A IC I3 (in relation to A C P ) used in the reaction, which was less than the stoichiom etric am ount normally required.

7 Fig. 5.1 shows the time dependence o f the conversion o f A C P (wt.%) over SZ, ST, H- beta and A IC I3 under similar conditions. H-beta showed a lower initial activity com pared to SZ and A IC I3, because o f diffusional resistance in H-beta. However, after 2 h o f reaction time H-beta perform ed better than AICI3. The lower activity o f A IC I3 after 2 h may be attributed to the am ount o f A IC I3 (in relation to A C P ) used in the reaction, which was less than the stoichiom etric am ount normally required. The ST catalyst was considerably less active than SZ and A IC I3, because o f diffusional resistance in H-beta. Reaction time (h) Fig, 5.2. Effect o f reaction time on conversion (wt.%) o f ACP and dypnone selectivity (%) over SZ catalyst; Reaction conditions: catalyst (g)=0.5; acetophenone (mol) = 0.042; reaction tem perature (K) = 433. However, after 2 h o f reaction time H-beta perform ed better than A IC I3. The lower activity o f A IC I3 after 2 h may be attributed to the am ount o f A IC I3 (in relation to A C P ) used in the reaction, which was less than the stoichiometric amount norm ally required. The ST catalyst was considerably less active than H-beta and SZ due to its lower acidity and w eaker acid sites 122

(Table 5.1). Based on this conversion o f ACP after 1 h o f reaction time, positive trend in activities for the catalyst SZ was studied varying other reaction param eters. Fig. 5.2 shows the conversion o f A C P and product distribution over SZ w ith the increase in reaction tim e up to 10 h.

It can also be seen from the results that there is a steady increase in the conversion o f ACP and the yield o f dypnone, which level o ff after 3 h o f reaction time.

8 (Table 5.1). Based on this conversion o f ACP after 1 h o f reaction time, positive trend in activities for the catalyst SZ was studied varying other reaction param eters. Fig. 5.2 shows the conversion o f A C P and product distribution over SZ w ith the increase in reaction tim e up to 10 h. Reaction conditions were detailed in Table 5.2. It can also be seen from the results that there is a steady increase in the conversion o f ACP and the yield o f dypnone, which level o ff after 3 h o f reaction time. The result shows that the reaction tim e influenced the conversion o f ACP and product yields in the condensation o f ACP. 5.S.3. Influence o f catalyst/acp ratio on A C P conv. Vs reaction tim e Fig. 5.3 compares the conversion o f ACP as a function o f reaction time using different concentrations o f catalyst under similar conditions as those depicted in Table 5.2. The conversion o f ACP is found to increase markedly up to 2 h o f reaction time with the increase in SZ/ACP ratio from 0.05 to However, for longer reaction time (5 h) the conversion o f Reaction time (h) Fig Effect o f catalyst/acp ration on conversion o f ACP (wt.%); Reaction conditions; acetophenone (m ol) = 0.042; catalyst (g)=0.5; reaction tem perature (K) =

ACP is sim ilar at all catalyst concentrations. A negligible, low er conversion o f ACP (wt.% ) is observed in the absence o f catalyst. Fig. 5.4 shows the effect o f SZ (catalyst)/ ACP ratio (wt./wt.

9 ACP is sim ilar at all catalyst concentrations. A negligible, low er conversion o f ACP (wt.% ) is observed in the absence o f catalyst. Fig. 5.4 shows the effect o f SZ (catalyst)/ ACP ratio (wt./wt.) on the conversion o f ACP, rate o f ACP conversion and product distribution. The catalyst/acp ratio was varied from 0.05 to 0.15 by keeping the concentration o f ACP constant. The total surface area available for the reaction depends on the catalyst loading. It was found that with an increase in catalyst/acp ratio the conversion o f ACP increases linearly from 17.2 to 30.7 wt. % for the reaction time o f 1 h. The reason is due to the increase in the total num ber o f acid sites available for the reaction. 100 i i E T 75 i " I? I 50 Conv. Rate Dyp. Others a 25 9 D o a Catalyst (S04^7Zr02)/ACP (wt./wt.) Fig Effect o f catalyst/acp ration on conversion o f ACP (wt,%), rate and product distribution (wt.%); Reaction conditions: acetophenone (mol) = 0.042; reaction tem perature (K) = 433; reaction time (h) = 5. The corresponding rate decreases from 28.7 to 17.1 m m olg''h ' respectively. No change in the dypnone selectivity is observed with the change in catalyst/a C P ratio. These results indicate 124

the need o f a catalyst for decreasing the activation energy barrier in the condensation o f ACP to dypnone. 5.

10 the need o f a catalyst for decreasing the activation energy barrier in the condensation o f ACP to dypnone Influence o f reaction temp, on ACP conv. Vs reaction tim e Fig. 5.5 shows the effect o f the reaction tem perature on the conversion o f ACP Vs reaction tim e during the condensation of ACP. The reaction tem perature was varied between 403 K and 433 K. Increasing the reaction tem perature increases the catalytic activity sharply up to 3 h o f reaction time and the conversion o f ACP levels off with reaction time at all reaction tem perature studied. The effect o f reaction tem perature on the conversion o f ACP, rate o f ACP conversion and product distribution is investigated in the range o f K Reaction time (h) Fig. 5.5 Influence o f reaction temperature (K) on the conversion o f ACP (wt.%) over SZ catalyst w ith reaction tim e ( h ) ; Reaction conditions: catalyst(g)=0.5; acetophenone(m ol) =

A maximum in dypnone selectivity (87 wt.% ) over this catalyst is observed at 403 K. The apparent activation energy for the condensation reaction over SZ is estim ated to be 40.8 kj mop'.

11 using the SZ as catalyst (Fig. 5.6). The conversion o f ACP and rate o f ACP conversion increases from 17.1 to 40.1 wt.% and 2.8 to 6.7 m m olg''h ' respectively, w hen the tem perature is raised from 403 to 433 K. However, the selectivity for dypnone rem ains nearly constant as shown in Fig A maximum in dypnone selectivity (87 wt.% ) over this catalyst is observed at 403 K. The apparent activation energy for the condensation reaction over SZ is estim ated to be 40.8 kj mop'. Reaction temperature (K) Fig Effect o f reaction temperature (K) on the conversion o f ACP (wt.%), rate o f ACP conversion (mmol g h '') and product distribution, over SZ catalyst; Reaction conditions: catalyst (g)=0.5; acetophenone (mol) = 0.042; reaction tim e (h) = C atalyst recycling SZ sample used in the condensation o f ACP was recycled two times (Fresh+ two cycles). Fig. 5.7 presents the results of these experiments. The catalyst shows a m arginal decrease o f the activity after the use o f fresh catalyst. H ow ever, after first recycle o f the 126

others e -D %*- i O 40 CL 20 O -o > C C TO o u n m Fresh [MI} First FMI Second Recycling Fig. 5.7. Effect o f recycling of catalyst (SZ); Reaction conditions; catalyst (g)=0.5; acetophenone (mol) = 0.

12 catalyst, a m inor decrease in tiie catalytic activity was noticed without loosing its selectivity for dypnone. The present study indicates that the catalyst can be recycled a num ber o f times w ithout loosing its activity to a greater extent. 100 f i 80 ii 60 Conv. Rate Dyp. others e -D %*- i O 40 CL 20 O -o > C C TO o u n m Fresh [MI} First FMI Second Recycling Fig Effect o f recycling of catalyst (SZ); Reaction conditions; catalyst (g)=0.5; acetophenone (mol) = 0.042; reaction time (h) = M echanism The formation o f dypnone takes place when one o f acetophenone molecule gets protonated and forms its conjugate acid (Scheme 5.2, eq.l). The electrophilic addition o f the carbonium ion (conjugate acid) to the e n d form o f another m olecule produces aldol (Schem e 5.2, eq.2). Further protonation of the alcoholic OH o f the aldol and elimination o f water molecule forms a carbonium ion intermediate (Scheme 5.2, eq.3). Loss o f H" from the cx-c atom results in the formation of a, (3-unsaturated ketone (dypnone) (Schem e 5,2, eq.4). 127

$?\ 1 CgH,-C-C^-K:gH, ^ C g H j-c -C -C ------------ (eq.4) i i n. '3 '3 Scheme 5.2 dypnone 5.$ 4 Conclusions It is found that SZ and H-beta exhibit sim ilar activity (rate o f ACP conversion), which is higher than that o f sulfated titania.

4 Conclusions It is found that SZ and H-beta exhibit sim ilar activity (rate o f ACP conversion), which is higher than that o f sulfated titania.

13 n + ( j)h (ph CsHg-C-CHa ^ ' ^ CgHg-C CH3 ^ -- CgH f CH3 (eq.1) acetophenone '? < " ; = ^ ( e q 2 ) C,H,-C = C H, *C.H, q -C H, ^ enol form-acp aldol II H* 5? H C H 3 H C H 3 aldol O H.?\ 1 CgH,-C-C^-K:gH, ^ C g H j-c -C -C (eq.4) i i n. '3 '3 Scheme 5.2 dypnone 5.4 Conclusions It is found that SZ and H-beta exhibit sim ilar activity (rate o f ACP conversion), which is higher than that o f sulfated titania. From the TPD o f N H 3 it is seen that both sulfated zirconia and H-beta are highly acidic and possess strong acid sites, as seen from N H 3 desorption in the temperature range o f 513 K to 873 K, which are responsible for the reaction. The conversion o f ACP increases with reaction time, the catalyst concentration and reaction tem perature. The SZ is recycled two times to show that there is only a m arginal decrease in activity on recycled catalyst with no loss in the selectivity for dypnone. 128

5.5. References 1. W. Taylor, J. Chem. Soc. (1937) 304. 2. N. O. Callow ay and L. D. Green, J. Am. Chem. Soc. 59 (1937) 809. 3. H. Adkins and F. W. Cox, J. Am. Chem. Soc. 60 (1938) 1151. 4. J. H. Simons and E.

Venuto, M icroporous Mater. 2 (1994) 297. 8. P.B. Venuto and P.S. Landis, J. Catal. 6 (1966) 237. 9. T. Jaimol, P. M oreau, A. Finiels, A.V. Ram aswamy and A.P. Singh, Appl. Catal. A; G eneral 214 (2001) 1.

14 5.5. References 1. W. Taylor, J. Chem. Soc. (1937) N. O. Callow ay and L. D. Green, J. Am. Chem. Soc. 59 (1937) H. Adkins and F. W. Cox, J. Am. Chem. Soc. 60 (1938) J. H. Simons and E. O. Ramler, J. Am. Chem. Soc. 65 (1943) H. Garcia, J. C. M aria, A. Corma, S. Iborra and J. Primo, Appl. Catal. A: General ( )5. 6. H. P. Hagen, U.S. Patent (1984). 7. P.B. Venuto, M icroporous Mater. 2 (1994) P.B. Venuto and P.S. Landis, J. Catal. 6 (1966) T. Jaimol, P. M oreau, A. Finiels, A.V. Ram aswamy and A.P. Singh, Appl. Catal. A; G eneral 214 (2001) V.D. Chaube, P. M oreau, A. Finiels, A.V. Ram aswam y and A.P. Singh, J. Mol. Catal. A; Chem ical 174 (2001) C. V enkatesan, T. Jaimol, P. Moreau, A. Finiels, A.V. Ram asw am y and A.P. Singh, Catal. Lett. 75 (2001) A.P. Singh, S.P. Mirajkar, S. Sharma, J. Mol. Catal. A. 150 (1999) A. Corma, M.I. Juan-Rajadell, J.M. Lopez-Nieto, A.M artinez, and C. M artinez, Appl. Catal. A: General 111 (1994) A. P. Singh, D. Bhattacharya, and S. Sharma, J. Mol. Catal. A; Chem ical 102 (1995)

Multistep Synthesis of 5-isopropyl-1,3-cyclohexanedione

Multistep Synthesis of 5-isopropyl-1,3-cyclohexanedione The purpose of this experiment was to synthesize 5-isopropyl-1,3-cyclohexanedione from commercially available compounds. To do this, acetone and